Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
:
BASF Aktiengesellschaft 930589 O.Z. 0050/44856
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Preparation of radiation-curable acrylates
The present invention relates to a process for the preparation of
5 radiation-curable acrylates. EP-A-54 105, DE-A 33 16 593 and
EP-A-27 93 303 disclose processes in which, in a first stage, a
(meth)acrylate is prepared from (meth)acrylic acid and a hydroxy
compound and, in a second stage, excess (meth)acrylic acid is
reacted with an epoxide.
EP-A-280 222 (O.Z. 0050/38998), DE-A-23 46 424 and E~-A-211 978
disclose that the reactivity of acrylates can be increased by
adding compounds having primary and/or secondary amino groups.
The amino groups undergo addition at the double bonds of the
15 acrylates (Michael addition). In the case of the above acrylates
prepared in two stages, the addition of amine leads to a sharp
increase in the visc06ity, with the result that the requirement
for reactive diluents is increased to an undesirable extent.
20 It i~ an object of the present invention to provide a process for
the preparation of amine-modified acrylates in a two-stage pro-
cedure, ie. reaction of (meth)acrylic acid with a hydroxy com-
pound and subsequent reaction with an epoxide, in which the
reaction product has a very low viscosity.
We have found that this object is achieved by a process for the
preparation of radiation-curable acrylates, wherein, in a 1st
stage, a hydroxy compound is reacted with acrylic acid or meth-
acrylic acid and, in a 2nd stage, the reaction product of the 1st
30 stage is subsequently reacted with an epoxy compound and com-
pounds having one or more primary or secondary amino groups are
added in or before the 2nd stage and, after the addition of these
compounds, the reaction of the 2nd stage is continued until the
acid number of the reaction mixture has decreased by at least
35 3 mg KOH/g of reaction mixture from the time of addition of these
compounds.
We have also found the acrylates obtained by this process and
their use in coating materials.
In a 1st stage of the novel process, acrylic acid or methacrylic
acid (referred to by the overall term (meth)acrylic acid), pre-
ferably acrylic acid, is reacted with`a hydroxy compound.
Suitable hydroxy compounds are compounds having one or more
45 hydroxyl groups. Examples are monoalcohols, for example alkanols
or alkoxylated alcohols with a remaining OH group, C2-C~-alkylene-
diols, trimethylpropane, glycerol or pentaerythritol, or, for
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example, hydroxyl-containing compounds alkoxylated with ethylene
oxide or propylene oxide.
Preferred hydroxy compounds are saturated polyesters which con-
5 tain at least 2, in particular 2 to 6, free hydroxyl groups and
may also contain ether groups, or polyethers having at least 2,
in particular 2 to 6, free hydroxyl groups.
The molecular weights Mn of the polyesters or polyethers are pre-
10 ferably from 100 to 4000 (Mn determined by gel permeation chroma-
tography).
Such hydroxyl-containing polyesters can be prepared, for example,
in a conventional manner by esterification of dicarboxylic acids
15 or polycarboxylic acids with diols or polyols. Starting materials
for such hydroxyl-containing polyesters are known to a person
skilled in the art.
Succinic acid, glutaric acid, adipic acid, sebacic acid,
20 o-phthalic acid, isomers and hydrogenation products thereof and
esterifiable derivatives, such as anhydrides, eg. maleic
anhydride, or dialkyl esters of the stated acids may preferably
be used as dicarboxylic acids. Examples of polycarboxylic acids
and their anhydrides are trioic or tetraoic acids, such as tri-
25 mellitic anhydride or benzenetetracarboxylic acid.
Preferred diols are ethylene glycol, 1,2- and 1,3-propylene
glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclo-
hexanedimethanol and polyglycols of the ethylene glycol and
30 propylene glycol type.
Examples of polyols are primarily trimethylolpropane, glycerol
and pentaerythritol.
35 other suitable diols or polyols are diols or polyols which are
oxyalkylated (for example with ethylene oxide or propylene
oxide), in particular having a degree of oxyalkylation of from 0
to 10, based on the particular hydroxyl groups of the diol or
polyol.
The polyesterols to be used according to the invention include
polycaprolactonediols and polycaprolactonetriols, the preparation
of which is likewise known to a person skilled in the art.
g5 Examples of suitable hydroxyl-containing polyethers are those
which can be obtained by known processes, by reacting dihydric
and/or polyhydric alcohols with various amounts of ethylene oxide
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and/or propylene oxide. Polymerization products of tetrahydro-
furan or of butylene oxide may also be used.
Preferred hydroxyl-containing polyethers are oxyalkylation
5 products of the abovementioned diols or polyols, in particular
having a degree of oxyalkylation of from 0 to 10, particularly
preferably from 1 to 10, based on the particular hydroxyl groups
of the diol or polyol, a total of at least 2 alkoxy groups,
however, being present in the polyether.
In the esterification of the (meth)acrylic acid in the case of
the hydroxyl-containing polyester, it is, for example, also
possible initially to take the (meth)acrylic acid together with
starting materials of the hydroxyl-containing polyester, for
15 example dicarboxylic acids or anhydrides thereof and diols or
polyols and to react the starting materials together with the
(meth)acrylic acid in one stage.
In the esterification of (meth)acrylic acid with the hydroxy com-
20 pound, preferably from 0.1 to 1.5, particularly preferably from
0.5 to 1.4, and very particularly preferably from 0.7 to 1.3,
- equivalents, based on 1 hydroxyl equivalent of the hydroxy com-
pounds, of (meth)acrylic acid are used. In the abovementioned
case where the starting materials, for example of the hydroxyl-
75 containing polyester, are used in the esterification, the numberof equivalents of the (meth)acrylic acid is based on the number
of hydroxyl equivalents theoretically re ~in;ng after the reac-
tion of the starting materials, for example the reaction of
dicarboxylic acids with diols or polyols.
The reaction of the (meth)acrylic acid with the hydroxy compounds
can be carried out, for example, in the presence of an acidic
esterification catalyst, eg. sulfuric acid or p-toluenesulfonic
acid, and in the presence of a hydrocarbon which forms an azeo-
35 tropic mixture with water, in particular to a conversion of, inparticular, at least 85~, preferably from 90 to 95~, of the
hydroxyl groups of the hydroxy compound, for example at from 60
to 140 C. The water of reaction formed is removed azeotropically.
Suitable hydrocarbons are aliphatic and aromatic hydrocarbons,
40 for example alkanes and cycloalkanes, such as n-hexane, n-heptane
and cyclohexane, aromatics, such as benzene, toluene and xylene
isomers, and special gasolines which boil within a range from 70
to 140 C.
45 In order to avoid premature polymerization, the reaction with
tmeth)acrylic acid is advantageously carried out in the presence
of small amounts of inhibitors. These are the conventional
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compounds used for preventing thermal polymerization, for example
of the hydroquinone, the hydroquinone monoalkyl ether, the
2,6-di-tert-butylphenol, N-nitrosoamine, the phenothiazine or the
phosphorous ester type. They are used in general in amounts of
5 from 0.001 to 2.0~, preferably from 0.005 to 0.5%, based on the
reaction in the first stage.
After the esterification, the solvent, for example the hydro-
carbon, can be removed from the reaction mixture by distillation,
10 under atmospheric or reduced pressure. The esterification
catalyst can be neutralized in a suitable manner, for example by
adding a tertiary amine or alkali metal hydroxide. Furthermore,
excess (meth)acrylic acid can be partially removed, for example
by distillation under reduced pressure. The reaction product of
15 the 1st stage generally still has an acid number above 25, in
particular from 35 to 100, mg KOH~g of substance ~without
solvent) before the beginning of the reaction in the 2nd stage.
In the 2nd stage, the reaction product obtained in the 1st stage
20 is reacted with an epoxy compound. Epoxy c~ ounds are those
having at least one epoxy group, preferably at least two, pre-
ferably two or three, epoxy groUpQ in the molecule.
For example, epoxidized olefins, glycidyl esters of saturated or
25 unsaturated carboxylic acids or glycidyl ethers of aliphatic or
aromatic polyols are suitable. Such products are commercially
available in large numbers. Polyglycidyl compounds of the
bisphenol A type and glycidyl ethers of polyfunctional alcohols,
for example of butanediol, of glycerol and of pentaerythritol,
30 are particularly suitable. Examples of such polyepoxy compounds
are ~Epikote 812 (epoxide value: about 0.67) and Epikote 828
(epoxide value: about 0.53) and Epikote 162 (epoxide value: about
0.61) from Shell.
~5 The epoxy compounds are added in amounts of from 1 to 20,
particularly preferably from 5 to 15, ~ by weight to the reaction
product obtained in the 1st stage. The epoxy compounds are very
particularly preferably used in roughly equimolar amounts, based
on the number of acid equivalents that are still present in the
40 reaction product of the 1st stage.
In the reaction with epoxy compounds in the 2nd stage, acid which
is used in excess or is unconverted, in particular (meth)acrylic
acid, as well as, for example, dicarboxylic acid still present as
45 starting material in the mixture or resulting half-esters of
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dicarboxylic acids having a remaining acid group are bound as
epoxy esters.
The reaction with epoxy compounds is carried out at preferably
5 from 90 to 130 C, particularly preferably from 100 to 110 C, and
preferably until the reaction mixture has an acid number of less
than 5 mg KOH/g.
For example, quaternary ammonium or phosphonium compounds,
10 tertiary amines, phosphines, such as triphenylphosphine, or Lewis
bases, such as thiodiglycol, may be used as catalysts for the
reaction of the epoxy compounds with the acid groups in the 2nd
stage.
15 The catalysts are preferably used in amounts of from 0.01 to 5,
particularly preferably from 0.1 to 3~ by weight, based on the
epoxy compounds.
During the reaction with the epoxy compounds in the 2nd stage,
20 compounds having one or more primary or secondary amino groups
are added to the reaction mixture.
The number of amine hydrogen atoms (N-H) of primary or secondary
amines in the case of these compounds is preferably from 1 to 6,
25 preferably from 2 to 4.
For example, the number of amine hydrogen atoms is 4 in the case
of a compound having two primary amino groups and 3 in the case
of a compound having one primary and one secondary amino group.
Primary or secondary amino groups undergo a Michael addition
reaction with acrylate groups:
H2C = C--C
~ o
__~ H3C - C - C
\ O--
/ \
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Primary amino groups thus become secondary amino groups, which in
turn can undergo addition with acrylate groups with formation of
tertiary amino groups.
5 Suitable compounds having primary or secondary amino groups are
generally low molecular weight compounds and preferably have a
molecular weight of less than 1000.
Examples are primary monoamines, such as C1-C20-alkylamines, in
10 particular n-butylamine, n-hexylamine, 2-ethylhexylamine and
octadecylamine, cycloaliphatic amines, such as cyclohexylamine,
and amines containing (hetero)aromatic groups, such as benzyl-
amine, l-(3-aminopropyl)imidazole and tetrahydrofurfurylamine.
15 Compounds having 2 primary amino groups are, for example, Cl- or
C2-alkylenediamines, such as ethylenediamine, butylenediamine,
neopentanediamine or hexamethylenediamine.
Other examples are 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxa-
20 tridecane-1,13-diamine, and 4,4'-diaminodicyclohexylmethane.
Examples of amines having hydroxyl groups are alkarolamines, eg.
ethanolamine, tert-propanolamine, aminoethoxyethanol, aminoethyl-
ethanolamine, 2-aminopropanol, 2-aminobutanol, etc.
25 Compounds having primary and secondary amino groups are, for
example, 3-amino-1-methylaminopropane, diethylenetriamine,
dipropylenetriamine and N,N'-bis(3-aminopropyl)ethylenediamine.
The compounds having one or more primary or secondary amino
30 groups are preferably used in amounts such that there is from
0.005 to 0.4, preferably from 0.1 to 0.3, mol of amine hydrogen
atoms of primary or secondary amino groups per mole of acrylate
groups.
35 The compounds having primary or secondary amino groups are added
to the reaction mixture in or before the 2nd stage, and the reac-
tion in the 2nd stage is then continued until, after the addition
of the compounds having primary or secondary amino groups, the
acid number decreases by at least 3, preferably at least 4, mg
40 KOHJg of reaction mixture from the time of addition of these com-
pounds.
The compounds having primary or secondary amino groups are pre-
ferably added at an acid number of the reaction mixture of from 8
45 to 80, particularly preferably from 9 to 35, mg KOH~g. The
addition is preferably carried out during the reaction in the 2nd
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stage. The latter reaction is then preferably terminated when the
acid number has decreased to below 5 mg KOH/g.
The radiation-curable acrylates obtainable by the novel process
5 have a low viscosity, with the result that in particular the
requirement for reactive diluents for establishing viscosities
suitable for processing is reduced.
The radiation-curable acrylates obtainable by the novel process
10 are particularly suitable for use as or in materials which can be
cured thermally, but preferably by high-energy radiation.
The materials can be used as or in coating materials, for example
finishes, printing inks or adhesives, as printing plates, as
15 moldings, for the production of photoresists, in stereolitho-
graphy or as molding material, for example for optical lenses.
For use as or in radiation-curable materials, for example, addi-
tives such as crosslinking agents, thickeners, leveling agents or
20 fillers or pigments, etc., may be added to the radiation-curable
acrylates (referred to below as radiation-curable composition).
Particularly suitable crosslinking agents for the subsequent
crosslinking are isocyanate compounds. Suitable isocyanate com-
25 pounds have at least 2 isocyanate groups.
The radiation-curable acrylates and their compositions can be
cured thermally, preferably by high-energy radiation, such as UV
light or electron beams.
For radiation curing by UV light, photoinitiators are usually
added.
Examples of suitable photoinitiators are benzophenone and deriva-
35 tives thereof, such as alkylbenzophenones, halomethylated benzo-
phenones and Michler's ketone, as well as benzoin and benzoin
ethers, such as ethylbenzoin ether, benzil ketals, such as benzil
dimethyl ketal, acetophenone derivatives, eg. hydroxy-2-methyl-
phenylpropan-1-one and hydroxycyclohexyl phenyl ketone, anthra-
40 quinone and its derivatives, such as methylanthraquinone, and inparticular acylphosphine oxides, such as Lucirin~ TPo (2,4,6-tri-
methylbenzoyldiphenylphosphine oxide).
The photoinitiators, which, depending on the intended use of the
45 novel materials, are used in amounts of from 0.1 to lS, pre-
ferably from 1 to 10, % by weight, based on the polymerizable
components, may be employed as individual substances or, owing to
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frequent advantageous synergistic effects, in combination with
one another.
Examples
I Stabilizers and 6.05 g of sulfuric acid were added to 562.8 g
of dipropylene glycol, 204.4 g of adipic acid, 443.5 g of
acrylic acid and 403 g of methylcyclohexane, and the mixture
was heated to 100 C. 152 ml of acrylic acid-containing water
(acid number 175.3 mg KOH/g) were removed in the course of 5
hours. The solvent and excess acrylic acid were distilled off
until the acid number reached 44.1 mg KOH/g. 154.8 g of
bisphenols A diglycidyl ether (Epikote~ 828) and 22.9 g of
tributylamine were then added at 107 C. Three portions a) to
c) of 310 g each were removed from the batch, and the reac-
tion mixtures were then each kept at 107 C for 4.5 hours,
in batch a) 9.3 g of ethylenediamine being added at an acid
number of 17.1 mg KOH/g (after a reaction time
of 1.5 hours),
in batch b) 9.3 g of ethylenediamine being added at an acid
number of 9.6 mg KOH/g (after a reaction time of
2.5 hours) and
in batch c) 9.3 g of ethylenediamine being added at an acid
number of 4.9, after 4.5 hours had elapsed.
The viscosities of the end products are listed in Table 1.
Table 1
Acid number Acid number after end of Viscosity/Pa.s
on addition the reaction in the 2nd
of amine stage
I a) 17.1 6.7 11.8
I b) 9.6 4.4 17.6
I c)* 4.9 2.6 58.2
* for comparison
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g
II Example II was carried out as I but with the following
starting materials:
748.8 g of tripropylene glycol, 189.8 g of adipic acid,
411.8 g cf acrylic acid, 450.0 g of methylcyclohexane, 6.75 g
of sulfuric acid, 25.6 g of tributylamine and 165.6 g of
Epikote 828; addition of 7.75 g of ethylenediamine in each
case to 310 g of intermediates of stage 1.
The viscosities of the end products are listed in Table 2.
Table 2
Acid number Acid number after end of Viscosity/Pa.s
on addition the reaction in the 2nd
of amine stage
II a) 15.6 6.2 7.1
20 II b)9.8 4.3 8.5
II c)* 3.7 2.7 18.6
* for comparison
